Azo-dyestuff and process of making same



Patented Sept. 13, 1932 UNITED STATES PATENT OFFICE FRITZ STRAUB ANDWALTER ANDERAU, OF BASED, SWITZERLAND, ASSIGNORS TO FIRM OE SOCIETY OFCHEMICAL INDUSTRY IN BASLE, OF BASED, SWITZERLAND AZO-DYESTUFF ANDPROCESS OF MAKING SAME e No Drawing. Application filed June 10, 1930,Serial No. 460,283, and in Switzerland June 12, 1929.

This invention relates to thefmanufacture of new azo-dyestuil's.It-comprises the proo ess of making these dyestuffs, the new dyestuffsthemselves, as well as the materlal dyed therewith.

According to this invention valuable azodyestuffs containing an azinenucleus are obtained by coupling at least one molecular proportion of adiazo-compound of the general formula wherein It stands for an arylresidue which may contain substitu.ents,w1th an azine WlllCll isobtained by treating with acids the azodyestuffs of the general formulain which R and B stands for aryl residues which may containsubstituents, one y is an OH-group and the other 2 a hydrogen atom, onea an SO H-group and the other 2 a hydrogen atom, the SO H-group and theOH-group being in meta-position to each other.

If the diam-compounds which are to come into use derive from compoundsof the general formula in which :0 stands for such a group inorthoposition to the -N=N-OH residue which, in combinationwith theazo-ohromophore of the dyestufl", imparts to the latter the capabilityof binding metals adapted to, form lakes, and in which R stands for anaryl residue, which may contain further substituents, the azo-dyestufiswhich are obtained after the coupling with the said azines may yet betreated with agents yielding metals capable of forming lakes.

Azines of the stated kind may be made from an N-substituted2-amino-5-hydroxynaphthalene-'T-s-ulfonic acid or from an N- substituted2-amino-8-hydroxynaphthalene- I 6-sulfonic acid, by coupling adiazo-compound in an acidmedium and treatin g with an acid theortho-amino-azo-dyestuif thus obtained. Among other compounds thefollowing N-substitution products of 2-amino-5-hydroxynaphthalene-7-sulfonic acid or 2- amino 8 hydroxynaphthalene 6sulfonic The azines can be coupled with any diazocompound. Azines whichcan be coupled twice, may be treated once or twice with the same or withdifferent diam-compounds.

The dyestuiis may be produced on the fibre, in which case it isadvantageous to pad the fibre with the azine in the form of itsleuco-compound and, after oxidation, to develop the dyeing withthediazo-compound. l

Dyestuiis which show mordant properties can be treated in substance, inthe course of their manufacture, in the dye-bath or on the fibre with anagent yielding metal, whereby conversion into the metal compound mayoccur whether in acid, neutral or alkaline medium, with or without asuitable addition,

and at ordinary pressure or under increased 5 pressure. The metals whichare suitable for the present processare those which can form complexes,for instance those Which have the atomic Weight 27 to 66, such as, forexample, chromium, copper, iron, cobalt or nickel.

It is also possible to obtain dyestuffs containing several metals. Theproducts of the invention may be used for dyeing wool, silk or cotton,viscose and varnishes.

The followingv example illustrates the manufacture of such azines whichare being used for the production of dyestuffs in accordance with thepresent. invention, the parts being by Weight vTo the diazo-compoundfrom 209 parts of sulfanilic acid there are added the freshlyprecipitated suspension, feebly acid with mineral acid, of 862 parts of2-ortho-carboxy-phenylamine-5-hydroXynaphthalene-7- sulfonic acid andthe mixture is stirred at r the ordinary temperature until the.diazocompound has pling is complete the whole is warmed on thewater-bath until a sample of .the dyestufl dissolved to a, pure. yellowsolution in dilute acetic acid. By adding 20-50parts of hydrochloricacid the formation of azine may be accelerated. When conversion iscomplete the liquid is nade alkaline with sodium disappeared. Whencoucarbonate and the sodium salt of the 2-sulfo-4-hydroxy-a-fl-naphtho-8-carboxy-phenazine of the probable formula isoan to a green-blue'solution. Alkaline reducing agents convert theproduct into the dihydroazine which is soluble to a yellow solution. Theazine is capable of coupling with diazocompounds.

The reaction may be extended to the various homologues of the2-arylamino-hydroxynaphthalene-sulfonic acid series.

The following table shows the properties 9 of some of the azines whichare used for the production of dyestuffs according to the presentinvention r Reactions Nomenclature (Richter) and Parent materialconsmunm cnaooon HOl 10 Soda Vat 5 E3 1 10 per cent per cent 10 per centcent, NaOH Hated (1) 2 'sulfo 4 hydroxy a B 2-para' -l1ydroxy metaOrange Blue-red Red Blue-red Yellowish- Violetnaphtho- 10- hydroxy 9(11) carboxyphenylamino-5- V 1 orange. black carboxyphenazine. naphthol'7 sulfonic acid.

v N OH OH- O O OH N (2) 2 sulfo 4 hydroxy a B 2 pafa carboxyphenyl-Orange Red Red Red- Yellow Violet naphtha l0 carboxyphenazlne ammo 5-rnaphthol 7- sulfonic acid OOOH Reactions Nomenclature (Richter) andParent material c n titutl 11 5 omooon H0110 Soda fggg Vat 5 8; 5 10 percent per cent 10 per cent cent NaOH trated n} (3) 2 sulfo 4 hydroxy a fl2 para ethoxyphenyl Orange Red Red Orange Yellow Violetnaphtho 10 ethoxyphenaamino 5 naphthol 7 brown. zine snlfonic acid.

SO H

. N 011 v oaaao I U r m (4) 2 11 4 hydroxy a 2 ortho methoxyphe- OrangeBed pre- Orange Orange Yellow Green-blue naphtho 8 Inethoxyphenazine y q5 D clpltate 7 sulfomc acid SIQaH /2\ 2e 1 3 r J 11 9 8 I 6 a 95 K N/00113 (5) 2-sulfo l hydtoxy a ,3 2 ortho pai a -dimeth- Brownish-B1ue-red Reddish- Red Yellow Blackishnaphtho 8:10 dimethylphena y p e y5 aee o ange blue-viozine naphthol 7 sulfonic let S0311 a d 39 i (j OH 7N CH3 as G:

(5) 2 sulfo 4 hydroxy a 2 Ineta ehlorophenyl- Orange Brownish- Red RedYellow Violet naphtho-Q (11) -chlotophenazine 7 red 7 sulfomc acid Thefollowing examples illustrate the mansodinm carbonate in 450 parts ofwater. uiaoture and application of dyestuffs in ac- There are then added16 parts of sodium be cordance With the invention, the parts beingcarbonate and the temperature is reduced to by Weight 56 C. by meansofice,v.rl1erenpon the diazo- Example 1 compound from 12.3 parts ofortho-anisidine -33 1 1 j v htho 1S IDlZIOClHCOQl. After a short timethe cougg g fl g z ggz gfi Imp pling 1s finished and the dyestulif ofthe m: o formula du N I l N 30 I\N w soaz- H300 HOS a OH 7 are dissolvedwith aid of-5.5 parts of calcined may be filtered and dried. It is adark pow J E azample 2 30 parts of 2-sulfo-4-hydroXyx-;8-naphth0-phenazine are dissolved in .330 parts of water with aid of 25 parts ofcalcined sodium carbonate, and the solution is coupled at 810 G. withthe diazo-compound from 22 parts of 4 nitro 2- amino l-phenol-G-sulfonicacid. After some hours the coupling is complete and the dyestuff of theformula OH Hois- HOaS may be separated by salting out. It is a brownpowder soluble in dilute acetic acid to an orange solution. In dilutesodium carbonate solution it dissolves to blackish-brownviolet(dichroitic) solution and in concentrated sulfuric acid to a greensolution. It dyes wool in an acid bath blackish-green tints, whichbecome fast blaekish-violet'by aftertreatment with a copper salt and adark green on treatment with a chromium salt. Cotton is dyed in a bathalkaline with sodium carbonate grey tints, which yield a fast violet onIn the presafter-treatment with copper. ence of chromium salts cottonlsdyed olivegreen tints.

Ewample 3 The dyestufl' obtained as described in EX- :ample 2 isdissolved hot in 2000 parts of water and the solution is mixed with asolution of chromium fluoride corresponding with 16 parts of C130 thewhole being boiled for 24 hours, water being supplied from time to timein place of that evaporated. The new chromium compound may then besalted out. YVhen dry it is a blackish powder, soluble in water. toblackish-brownsviolet 1 solution, in

sodium carbonate solution of 10 per cent. strength to a blackish-greensolution and in concentrated sulfuric acid to an olive-brown solution.Wool and silk are dyed by this dye. stuff in an acid bath fast greentints. Cotton and artificialsilk of regenerated cellulose are dyed in aneutral bath or a bath alkaline with sodium carbonate green-grey tintswhich equalize well.

Ewample 4 The dyestuff from 33 parts of 2-sulfo l-'hydroxy-u-B-naphtho-phenazine and 22 parts of-nitro-2-amino-l-nheno-l-G-sulfonic acid described in EXample 2 isdissolved in 2000 parts of water and mixed, while hot, with 26 parts ofcrystallized copper sulfate. copper compound ofthe dyestuff is thenobtained by salting out. When dry it is a bronze powder which dissolvesin water and in dilute alkalies to a red-violet solution and inconcentrated sulfuric acid to a green solution. It dyes cotton andartificial silk of regenerated cellulose in a bath containing Glauberssalt, which may be neutral or alkaline with sodium carbonate, violettints.

if there be substituted for the 26 parts of copper sulfate an equivalentquantity of nickel suifate therewill be obtained the nickel compoundsimilar to the copper compound. This nickel compound dissolves in waterto a red-violet solution, in dilute alkalies to a brown-violet solutionand in concentrated sulfuric acid to a green solution, and dyes cottonin a bath containing Glaubers salt greenishviolet tints.

Instead of the naphtho-phenazine used in Examples 14 there maybe usedwith like results the 2-sulfo-t-hydroxy-a-fi-naphtho-10- tolazine. Thedyestuffs are very similar in tint and properties to those described.

Example 5 is isolated. l/Vhen dryit is a blackish powder soluble inwater to a brown-red solution, in

The

When coupling is dilute alkalies to a red solution and inconcentratedsulfuric acid to a green solution. It dyes Wool in an acid bathBordeaux-red tints which become faster when after-treated with copper;when after-chromed, the tint is a dark brown. On cotton, in presence ofa chromium there is obtained a brown shade. i

If in this example on completion of the coupling the dyestuff is boiledwith a solution of 25 parts of copper sulfate and filtered when cold,there is obtained the complex copper compound of the dyestuff. It is adark powder which dissolves in water to a red solution, in dilute sodiumcarbonate solution to a blue-red solution and in concentrated sulfuricacid to a green solution. It dyes vegetable fibres in a bath containingGlaubers salt, and alkaline with sodium carbonate or neutral, violettlnts.

E wamplc 6 4:? parts of 5 5dihydroxy-7 7 -disulfo-1:l'z2z2-dinaphthazine are dissolved in 500 parts of water with aid of10.5 parts of sodium carbonate and coupled in presence of sodiumbicarbonate and sodium acetate with the diaZo-compound from 44 parts ofit-nitro- 1--aminobenzene-2sulfonic acid. When coupling is complete, thelyestufi' of the formula is isolated by salting out and dried. It is adark powder soluble in water to a blue-red solution; in dilute sodiumcarbonate solution to a violet solution and in dilute caustic sodasolution to ablue-violet solution. In concentrated sulfuric acid itdissolves to a green solution. It dyes wool in an acid bath reclbrowntints and cotton in a bath containing Glaubers salt and alkaline withsodium carbonate red-violet tints.

Example 7 47 parts of 5:5-dihydroxy-7:7-disulfo- 1:1:2:2-dinaphthazineare dissolved in 400 parts of water with aid of 40 parts of calcinedsodium carbonate, and the solution is coupled with the diazo-compoundfrom parts of 4-nitro-2-amino-l-phenol-G-sulfonic acid. -After somehours the azo-dyestufl' formed of the formula noa s N=N -s0=H -OH to. T\

noss- N=N- N02 may be salted out. lVhen dry it is a black powder,soluble in water to a blackish-green solution, in dilute alkalies to ablackish-green solution and in concentrated sulfuric acid to agreen-blue solution. It dyes cotton in a neutral bath containingGlaubers salt greengrey tints which become fast reddish-grey whenafter-treated with copper. In presence of chromium salts it dyes cottongrey-green. In an acid bath it dyes wool a blackish-green, which becomesfaster when after-chromed; when treated with copper the dyeing becomesgrey.

Example 8 The copper complex compound of the dyestuff of Example 7 isobtained by heating the dyestuff formed on completion of the couplingwith an ammoniacal solution of copper oxide made from 50 parts ofcrystallized copper sulfate. This complex copper compound is a blackpowder soluble in water to a reddish-violet solution, in dilute sodiumcarbonate solution to a blue-violet solution and in concentratedsulfuric acid to a bluegreen solution. It dyes cotton and artificialsilk of regenerated cellulose in a bath containing Glaubers salt, andneutral or alkaline, very fast grey equal tints. It dyes Wool in an acidbath grey tints.

E ammple .9

mium compound of the dyestufl' is obtained.

It is soluble in water to a grey blue solution, in dilute alkalies to agreen blue solution and in concentrated sulfuric acid to a greensolution. Cotton and artificial silk of regenerated cellulose are dyedin a neutral or alkaline bath containing Glaubers salt very level 1greenisltgrey tints On-Woolin'an acidibath the dyestulf yields greentints.

In place of the -nitro-2-amino-l-phenol- 6-sulfonic acid used as thediazotizing' com-' ponent in Example 79, there may be used tnitro-Q-amino-l-phenol. In this case dyestuffs are obtained Which havesubstantiallythe same properties and tints as those of the dyestuffsdescribed above. is somewhat smaller:

4-chloro-2-amino-1-phenol-6+sulfonic acid.

Ewample 1O I A grounding bath is prepared from 18 grams of 5:5-dihydroXy-7 7 -di s'ulfo-1 1 .2 2=dinaphthazine 50 cc..of causticsodasolution of e0 per cent. strength perlitre of liquor,

and the warm bathis reduced to dihydroazine by. means ofjgrams of sodiumhydrosulfite.

Cotton is handled under'the liquor in this .bath at room temperaturefor11; hour; It is .thenrinsed, .whereby the azineis re-oxidized: isDevelopment may thenfolloW in known man- ..ner by means of .a.neutralized Idiazo-compound-flWith paraenitrodiazobenzene there is-obtained a brown-olive ,tint,'. While With diazotized 2 .amino 4-.ch'lorobenzene-l 1-" phenylether an olive-brown dyeing is ob' tained.

IVhat We claim is 1. In the manufacture of metalliferous azo-dyes'tuffscontaining the azine nucleus,

the steplwhich comprises coupling at least onemolecular proportion of adiazo-com pound of the generalformula Wrerein It stands for a benzeneradiclev and mfor a lake-forming'. group in ortho-position to theazo-group, Withthe azines Which-are obtained by. treating Withacids theamdyestuffs of the general. formula V in'which R and R stand foraryl-radicles of-the benzene. and naphthalene series, one g isan.OI-Igr-oup and the other y a hydrogen :1 atom one .2 an O H-gnoup andthe other .2

a hydrogen atom, the SO H group andthe .OI-I-groupbeing. inmeta-position to each .other.

2. In the...manu-facture of metalliferous' azo-dyestufi'scontaining theazine nucleus;- "mthe step which comprises coupling ataleast.

Their solubility- Instead of the nitroaminophenolsulfonic acid there maybe used one 'moleeular, proportion of a diazo-compound of. thegeneralformula I n N=n-on wherein" ad stands. for a lake-forming groupin orthoposition to the azo-group and R stands for a benzene radicleWith the v:azineswhich are obtained by treating with acids the. azo-dyestuffs of the general for 1 111113 in Which R and R stan'dfor arylradicles of thebenzene: and naphthalene series.

3. In the manufacture: of metalliferous azo-dyestuffs containing theazine nucleus, the step which comprises coupling at least one molecularproportion of a diazo-compound of the general formula wherein :2? standsfor a lake-forming group in -ortho-position to the azo group, and Rstands fora 'benzeneradicle With the azines Which' are-obtained bytreating With'acids the azodyestufis of the general formula III=NR1 nmsmm wherein vR-stands for a benzene radicle and the: OH-group stands inortho-position to the -azo-group,-With the azines Which are obtained bytreating With acids'the azo-dyestuffs of the general formula HOQS vSOaHinwhichi R stands for an aryl radicle of the benzenevand naphthaleneseries.

I. 5:. In-themanufacture of metalliferous azodyestuffs containing theazine nucleus, the

-.step.which comprises coupling two molecular proportions of a(haze-compound of the general formula on R 1 N=NOH wherein It stands fora benzene radicle and the OHgro-up stands in ortho-position to theaz0-group with the azines which are obtained by treating with acids thezo-dyestuifs of i the general formula H038 NH SOaH J/ l on on in which Rstands for an aryl radicle of the benzene and naphthalene series.

6. In the manufacture of a metalhferous azo-dyestuii' containing theazine nucleus, the

step which comprises coupling two molecular proportlons of (liazotizedi-mtro-Zannnolphenol-G-sulfornc acid of the formula with the azine whichis obtained by treating with acids the aze-dyestufi of the formula HOaS-NH SO3H.

tn (m 7. In the manufacture of metalliferous azodyestuffs containing theazine nucleus, the step which comprises treating with an agent yieldingmetal capable of forming lakes with the lake-forming groups of theazo-dyestuffs,

, the azo-dyestuffs which are obtained by cou- 1/ wherein R and R standfor aryl radicles of the benzene and naphthalene series, one 3/ l3 '1 anOH-group and the other T/ a hydrogen atom, one a an SO HgrQup and theother e a hydrogen atom, the SO H-group and the Off-group being in metaposition to each other.

8. In the manufacture of metalliferous azodyestuffs containing the azinenucleus, the step which comprises treating with an agent yielding metalcapable of forming lakes with the lake-forming groups of theazo-dyestuffs, the aze-dyestuffs which are obtained by coupling at leastone molecular proportion of a diazo-compound of the general formulawherein It stands for a benzene radicle and a; for a lake-forming groupin ortho position to the azo-group, with the azines which themselves areformed by treating with acids the azoclyestuifs of the general formulawherein R and R stand for aryl radicles of the benzene and naphthaleneseries.

9. in the manufacture of metalliferous azodyestuf s containing the azinenucleus, the step which comprises treating with an agent yielding metalcapable of forming lakes with the lake-forming groups of theazo-dyestuffs, the azo-dyestuifs which are obtained by coupling at leastone molecular proportion of a diazo-compound of the general formulawherein R stands for a benzene radicle and w for a lake-forming groupin'ortho position to the azo-group, with the azines which themselves areformed by treating with acids the azo-dyestuffs of the general formulawherein R stands for an aryl radicle of the benzene and naphthaleneserles.

10. In the manufacture of metalliferous size-dyestuffs containing theazine nucleus, the step which comprises treating with an agent yieldingmetal of the atomic weigl'it 27 to 66 capable of forming lakes with thelake-forming groups of the azo-dyestuffs, the azo-dyestufis which areobtained by coupling at least one molecular proportion of adiazo-compound of the general formula wherein R stands for a benzeneradicle and :0 for a lake-forinlng group in ortho-pos1t1on to theazo-group, with the azines which themselves are formed by treating withacids the azo-dyestuffs of the general formula OH OH wherein R standsfor an aryl radicle of the benzene and naphthalene series.

11. In the manufacture of metalliferous azo-dyestuffs containing theazine nucleus, the step which comprises treating with an agent yieldingmetal of the atomic weight 52 to 66 capable of forming lakes with thelakeforming groups of the azo-dyestuffs, the azodyestuffs which areobtained by coupling at least one molecular proportion of a diazocompound of the general formula wherein R stands for a benzene radicleand m for a lakeforming group in ortho-position to the azo-group, withthe azines which are formed by treating with acids the azo-dyestuffs ofthe general formula 3 R\N=NOH wherein R stands for a benzene radicle andw for a lake-forming group in ortho-position to the azo-group, with theazines which are formed by treating with acids the azo-dyestuffs of thegeneral formula wherein R stands for an aryl radicle of the benzene andnaphthalene series.

I OH

13. In the manufacture of metalliferous azo-dyestuffs containing theazine nucleus, the step which comprises treating with an agent yieldingmetal of the atomic weight 52 to 56 capable of forming lakes with thelake-forming groups of the azo-dyestuffs, the azo-dyestufi's which areobtained by coupling two molecular proportions of a diazocompound of thegeneral formula wherein R stands for a benzene radicle and theOI-I-group stands in ortho-position to the azogroups with the azineswhich are formed by treating with acids the azo-dyestuffs of the generalformula wherein It, stands for an aryl radicle of the benzene andnaphthalene series.

14. In the manufacture of a chromiferous azo-dyestufi containing theazine nucleus, the step which comprises treating with an agent yieldingchromium the azo-dyestuif which is obtained by coupling two molecularproportions of dia'zotized 4-nitr0-2-amino-L phenol-6-sulfonic acid ofthe formula HOaS N=N-OH with the azine which itself is formed bytreating with acids the azo-dyestuff of the formula N=NO-S 0311 15.Process for the manufacture of metalliferous azo-dyestuffs containingthe azine nucleus, consisting in coupling at least one molecularproportion of a diazo-compound of the general formula wherein R standsfor a benzene radicle, and at for a lake-forming group in ortho-positionto the azo-group with the azines which are -i' formedby treating withacids the azo-dyestufis of the generalformula N=N--n1 wherein R and Rstand for aryl radicles,

of the benzene and naphthalene series, one 9 is an OH-group and theother 3 a hydrogen atom, one a an SO H-group andthe others a hydrogenatom, the sogH-group and the OH-group being in meta-position to eachother, and then treating the azo-dyestufi's containingthe azine nucleusthus obtained with agents yielding metal capable of forming lakes withthe lake-forming groups of the azo-clyestufis.

16. Process for the manufacture of metalliferous azo-dyestuifscontaining the azine nucleus, consisting in coupling at least onemolecular proportion of a diazo compound of the general formula N=N0Hwherein R stands for a benzene radicle, and a? for a lake-forming groupin ortho-position to the azogroup,- with-the azineswhicli are formed bytreating "with acidsthe azodyestuffs of the general formula f ITT==NR1wherein Rjand R stand for aryl radicles of the benzene and naphthaleneseries, and then treating the azo-dyestulf's containing the azinenucleus thus obtained with agents yielding metal capable of forminglakes with'the lake-forming groups of: the azo-dyestuffs= 17 Process forthe manufacture ofimetal liferous azo-dyestuffs containing the azinenucleus, consisting in. coupling-at least one molecular proportion of adiazo-compound of the general formula I H i N=N--o11 wherein R standsfor a-benzene radicle, and

. a: for a lake-forming group in ortho-position to the azo-group, withthe azines which are formed by treating with acids the azo-dyestufls ofthe general formula V i i V N=N-R1n a i i on a wherein R stands foranaryl radicleof the benzene and naphthalene series, andthen formed bytreating with l acids the azo dyev stuffs of the generahformula H 1-I=N-Ri n H wherein R stands for an aryl radicle of the benzene andnaphthalene series, and then treating the azo dyestufis containing theazine nucleus thus obtainedwith agents yielding metal of the atomicweight 27' to 66 capable of forming lakes withthelake-forming groups ofthe a-zo dyestulfs.

.19. Process forthe manufacture of metalliferous azo-dyestuffscontaining the azine nucleus, consisting in coupling at least onemolecular proportion of a diazo-compouncl of the general formula a i R i7 N==N-OH wherein R standsfor a benzene radicle, and for a lake-forminggroup in ortho-positiomtothe azo-group, with the azines which areforinedby treating with acids the amdyestuffs of the general formulawherein R stands for an aryl radicle of the benzene and naphthaleneseries, and then treating the azo-dyestuifs containing the azine nucleusthus obtained with agents yielding metal of the atomic weight 52 to 66capable ofzforming lakes with the lake-forming groups of theazo-idyestulf's.

20. Process for. the manufacture of metalliferous azo dyestuffscontaining the azine nucleus, consisting-in coupling at least onemolecular proportion of a di'a'zo-compouncl V of the general formulaN==N-OH wherein R stands for a benzene radicle, and wfor alake-formmggroup 1n ortho-positlon to the azo-group,with the azineswhich are formed by treating With acids the azo-dyestuffs of the'generalformula' wherein R stands for an aryl radicle of the benzene andnaphthalene series, and then vtreating the azo-dyestuiis containing theazine nucleus thus, obtained with agents yielding metalof the atomicweight 52 to 56 capable of forming lakes with the lake-forming groups oftheazo-dyestuffs. r

21. Processfor themanufacture of metalliferous azo-dyestuffs containingthe azine nucleus,vconsisting in coupling two molecular proportions of adiazo-compound of the general formula wherein stands-for a benzeneradicle and the OHi-group stands in ortho-position to the a zoegroup,with the. azines which are formed; by treating with acids theamdyestufl's of the general formula l 0,11 OH v wherein R stands foranaryl radicle of the benzene'and napththalene series, and then treatingthe azo-dyestufi's' containing the azine nucleus thus obtained withagents yielding metal of the atomic weight 52 to 56 capable of forminglakes with the lake-forming groups of the azo-dyestufls.

22. Process for the manufacture of a chromiferous azodyestufl containingthe azlne nucleus,. cons1st1ng in coupling tWo molecular proportions ofdiazotized l-nitro 2-amino-l-phenol-6-sulfonic acid of the formula N02with the mine which is formed by treating the azo-dyestufi of theformulaj on on with acids, and then treating the azo-dyestu'li containingtheazine nucleus thus'obtained with an agent yieldingchromium 23. As newproducts the metal compounds of the azo-dyestuffs containing the azinenucleus, which azo dyestuiis are obtained by 1 coupling at least onemolecular proportion of a dlazo-compound of the general formula N=NOHwherein R stands for a benzene radicle, and as for a lake-forming groupin ortho-position to the azo-group, with the azines which themselves areformed by treatingwith acids the azo-dyestufi's of the general formulawherein R and R stand foraryl radicles of the benzene and naphthaleneseries, one y is an OH-group and the other y a hydrogen atom, one a anSOgH group and the other 2 a hydrogen atm,.the SO H-group and theOH-group being in meta-position toeach other,'which products form blackto brown powders which dissolve in concentrated sulfuric acid toblue-green to green to olivebrown solutions, dyeing vegetable and animalfibres violet to green to grey tints.

24. As new products themetal compounds :1

VN=N-B1 HOsS- NHR2 wherein and R5 stand for aryl radicles of the benzeneand naphthalene series, which products form black to brown powders whichdissolve in concentrated sulfuric acid to blue-green to green to olivebrown solutions, dyeing vegetable and animal fibres violet to green togrey tints.

25. As new products the metal compounds of the azo-dyestufls containing'the' azine nucleus, which azo-dyestufls are obtained by coupling atleast one molecular proportion of a d1azo-compound of the generalformula wherein R stands for a benzene radicle, and m for a lake-forminggroup in ortho-position to the azo-group, with the azines whichthemselves are formed by treating with acids the azo-dyestulfs of thegeneral formula wherein R stands for a benzene radicle, and

00 for a lake-forming group in orthoposition to the azo-group, with theazmes which themselves are formed by treating with acids theazo-dyestuffs of the general formula l ll=N-Ri Ho3s NH son1 wherein Rstands for an aryl radicle of the benzene and naphthalene series, whichproducts form black to brown powders which dissolve in concentratedsulfurlcacid to bluegreen to green to olive-brown solutions, dye-N=N--0H wherein R stands for a benzene radicle, and

m for a lake-forming group in ortho-position to the azo-group, with theazines which themselves are formed by treating with acids theazo-dyestuffs of the general formula OH OH wherein R stands for an arylradicle of the benzene and naphthalene series, which products form blackto brown powders which dissolve in concentrated sulfuric :acid tobluegreen to green to olive-brown solutions, dyeing vegetable and animalfibres violet togreen to grey tints.

l 28. As new products the metal compounds of the azo-dyestuffscontaining the azine nucleus and metals of the atomic weight of 52 to 56capable of forming lakes with the lake-forming groups of theazo-dyestuffs, which azo-dyestulfs are obtained from coupling twomolecular proportions of a diazocompound of the general formula whereinR stands for a benzene radicle, and w for a lake-forming group inortho-position to the azo-group, with the azines which themselves areformed by treating with acids the azo-dyestuffs of the general formulaHOaS- NH soar OH OH wherein R stands for an aryl radicle of the benzeneand naphthalene series, which products form black to brown powders whichdissolve in concentrated sulfuric acid to blue green to green toolive-brown solutions, dyein g vegetable and animal fibres violet togreen to grey tints.

V 29. As new products the metal compounds of the azo-dyestuffscontaining the azine nucleus and metals of the atomic weight of 52 to 56capable of forming lakes with the lakeforming groups of theazo-dyestufls, which azo-dyestufls are obtained by coupling twomolecular proportions of a diazo-compound of the general formula whereinR stands for a benzene radicle, and

the OH-group 1n ortho-pos1t1on to the amgroup, "ith the azines whichthemselves are formed by treating with acids the azo-dyes stufls of thegeneral formula N=NR1 wherein R stands for an aryl radicle of thebenzene and naphthalene series, which products form black to brownpowders which dissolve in concentrated sulfuric acid to bluegreen togreen to olive-brown solutions, dyeing Vegetable and animals fibresviolet to green to grey tints.

30. As a new product the chromium compound of the azo-dyestuffcontaining the azine nucleus, which azo-dyestuff is obtained by couplingtwo molecular proportions of diazotizedl-nitro-2-amino-l-phenol-(i-sulfonie acid of the formula with the azinewhich is itself formed by treating the azo-dyestufi' of the formula Withacids, which product forms a black powder which dissolves inconcentrated sulfuric acid to a green solution, dyeing the vegetable andanimal fibres green-grey to green tints.

In witness whereof we have hereunto signed our names this 31st day ofMay, 1980.

FRITZ STRAUB. WALTER ANDERAU.

